Production of chlorates and chlorites of different metals



Nov. 29, 1949 C. A. HAMPEL PRODUCTION OF CHLORATES AND CHL ORITES OFDIFFERENT METALS Filed April 2, 1946 Cl 02. C L 02. 2 W Aesoease -HAasoeane K6103 /(CL 0;

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"4 [VAPOR/1 role 3; l/RRY I'll use awe/whom (ll/fifd/Zflhlfi l PatentedNov. 29, 1949 PRODUCTION OF CHLORATES AND CHLO- RITES OF DIFFERENTMETALS Clifford A. Hampel, Harvey, Ill., assignor to Cardox Corporation,Chicago, Ill., a corporation of Illinois Application April 2, 1946,Serial No. 659,043

13 Claims. 1

: This invention relates to a new process for the production of achlorate and a chlorite.

It has been known heretofore that a chlorate and a chlorite of the samemetal can be produced by the absorption of chlorine dioxide by analkaline compound of that metal. For example, if potassium chlorate andpotassium chlorite 'are to be produced, potassium hydroxide has beenemployed as the alkaline compound. The equation which illustrates thisreaction is:

This prior known process has possessed several inherent disadvantages.For example, there may be numerous commercial and economic reasons why aparticular manufacturer may want to produce for use or sale a chlorateand a chlorite of a different metal. To accomplish this desired resultwith the prior known process, it isnecessary to carry out this processtwice, using one metal alkali to produce-the. desired chlorate in oneprocess operation and usinganother metalalkali in the second processoperation to produce the desired chlorite of that metal. Therefore, fourproducts are formed, although only two really are desired. f

Another inherent disadvantage of the prior known process is that it isoften extremely difilcult or even impossible to efiect by practicalcommercial means the separation of the chlorate and the chlorite of thesame metal. fConsequently, after practising two different processes toobtain four products, only two of which'are really desired, themanufacturer has been confronted with the additional problem ofseparating out the two desired products.

Still another disadvantage of the prior known process is that the metalintroduced appears half as the chlorate and half as the chlorite. Thisis objectionable .if the metal is an expensive one as potassium, becauseit may be desired that all of it appear as the chlorate. I

It is a primary object of this invention to provide a process for theproduction of a chlorate and a chlorite of a different metal in whichthe chlorate and the chloritecan be selected in accordance with theparticular commercial needs of a given manufacturer.

It is a further important object of this invention to provide a processby means of which a desired chlorate and a desired chlorite can beproduced, and in which the chlorate and the' chlorite thus produced canbe obtained by the use of less expensive materials than thecorrespending metal base or bases.

A further primaryobject of this invention is to provide a process bymeans of which a chlorate and a. chlorite of a different metal arepro-.-

duced and which are readily separable by known commercial facilities. 1Aspecific object of this invention is to provide amethod of producing achlorate and a chlorite of a different metaLjin which one or the otheris considerably, less soluble in the same system, thus making them morereadily separable. Another specific object of the invention is toprovide a process for producing a chlorate and a chlorite of a differentmetal in which substantially all of a-particular cation introduced intothe, system, and which is capable of forming the chlorate or chlorite,is utilized in the production of the chlorate or chlorite which isdesired.

Another specific object of the invention is to provide aprocess for theproduction of a chlorate and a chlorite of adifierent metal by whichcer-- tain raw materials can be employed for producing one of thedesiredproducts which are different. from and less expensive than thebase which is normally employed to produce that product. The use of lessexpensive materials is made possible by employing the salt of the metalof the desired chlorateon-chlorite, which salt is less expensive thanthe corresponding base, and the base of the metal of the chlorate orchlorite de-' sired, whereby the .thus combined salt and base materialswill introduce only a foreign anion, which anion will form a salt withthe base cation which is less soluble in the system than the chlorateand/or chlorite produced. Other objectsand. advantages of the inven tionwill become'apparent during the course ofthe following-description:

' ,As has been pointed out above, and as is specifically illustrated inEquation a, it has been known that thechlorate and chlorite of a givenmetal can be produced by reacting chlorine di oxide with the baseof thatmetal. In accordance with thepres'ent invention, substantiallyequivalent quantities of a chlorate and a chlorite of difierent metalsareproduced. For example,

potassium, sodium, lithium, barium, calcium} salt or salts to theproducts of the first reaction. The process may be carried out indifferent ways, but they have in common the fact that the salt or saltswhich are added, are introduced into the system after the interactionbetween the chlorine dioxide and the metal base is substantiallycompleted and before any separation of the prod-- ucts of thatinteraction is effected. Also, although different procedures andingredients may be employed in practicing the invention, they have thecommon advantage that all or substan-, tially all of one of the metalswhich is introduced... appears either as the chlorate or the chlorite.

That the results of the present invention. can be obtained by thissubsequent addition of oer-- tain ingredients to the system, issurprising because of the large number of components which;- are in thesystem. It would be expected that due to the large number of componentsin the system, it would not be possible to obtain a defini-te setofproducts, but in carrying out the present invention it hasz been foundthat the same high percentage of products is formed which would beformed if a prior separation'hadbeen carried out with respect to. theproducts immediately resulting from the chlorine dioxide absorption.

One mode of carrying out the process of the present invention is tofirst absorb chlorinedioxide in an alkali which" has the-metal of thedesired chlorite but not that of the desired chlorate, the metal of thedesired chlorate beingintroduced as a salt. It may be pointed out herethat an important advantage of this procedure is that an alkali may beemployed which is considerably less expensive than the alkali whichwould have to be employed if the desired chlorate were to be produced bythe process represented by equation (a). For example, if it is desiredto produce potassium chlorate, instead of utilizing a relativelyexpensive potassium. alkaline compound, the invention comprehends theemployment of a sodium alkaline compound forthe production of thechlorate ion. After thereaction has proceeded until the alkali has beenneutralized and sodium chlorate and sodium chlo-- rite have beenproduced, a potassium salt is added to these mixed reactionproducts andthis will result in the formationof" the desired potassium chlorate. bytheequations:

In equation (b), sodium hydroxide is used, but? it is to beunderstoodthat any alkali; as an oxide,- hydroxide, or carbonate may be.employed-the hydroxide being used for illustrative purposes.

The term hydroxide as used in the claims embraces the introduction of;oxides of the named metals into the system since oxides will inherentlyform the hydroxides of the named metals in an aqueous medium. Also, itis to. be understood that the metal of this alkali should be that of thedesired chlorite and for this reason it may be any one of the alkalimetals, alkaline earth metals, or magnesium, sodium being selectedmerely to illustrate one exampleof the invention; Inaddition, it shouldbe understood that the salt used to introduce the metal of thedesiredchlorate need not be a chlorite as shown in equaetion 0, but mayhave another anion as, for: example, the sulfate, phosphate, or nitrateion. The metal of this salt. should,.however, be that; of the desiredchlorate and this may be a dif- These reactions are represented 4 ferentmetal selected from the above class from which the metal of the alkaliis selected.

It will be observed from Equations b and c that the salt which is addedfor the purpose of introducing the metal ion, whose chlorate is desired,should be added in an amount equivalent to one-half of the alkali whichis reacted. By adding this relative quantity of the salt having themetal whose chlorate is desired, its cation is present in an amountequivalent to the amount 7 of chlorate ion which is formed from thechlorine dioxide. Thus, as will appear from a combination of Equations band c, all of the potassium ion andall of the chlorate ion which is inthe system will be'combinedtoform potassium chlorate.

None of this metal of the introduced salt will, therefore, appearv asthe chlorite, and none of the chlorate ion which is formed will carrywith it a cation other than that of the introduced salt. In obtainingcertain chlorates, it is necessary to observe certain precautions in theselectionof the ingredients. For example, the potassium ion should notbe introduced into the system, if the chlorate of. some other metal isdesired. Also,- the salt used should not be a sulfate, for example, if.the chlorate desired is. that. of calcium or. barium.

If a chlorite is to, be utilized in carrying out the process representedby Equations b and c, this. chlorite may beobtainedi by carrying out asepa... rate chlorine dioxide absorption reaction. After the alkali usedin this separate absorption reaction isneutralized,-and before anyseparation of the reaction products is effected, they are combined withthe reaction products resulting from the first absorption reaction. Thisis represented by the equations:

FromEquations d, e, and it will be observed. that. equal-amounts. on. anequivalent basis of thewtwo alkalis. are employed. This results'in theproductionof. equivalent amounts of chlorate? and chlorite. ions in theseparate absorption re.-- actions, so that all of the one metal will.appear: asrthe chlorate and all of the other metal will appear as.thechlorite- It is not necessary that. thealkalis. employedv inEquations (1 and. e have; the same anion, as, for example, one may be a.hydroxide and. the. other may be a carbonate; The precaution referred toin connection with: Equations. b, andc should, however, be observed:in,the. selection of the anions and cations.

If, in. carryingout the process according to Equations b and.c,.. theintroduced salt is not. a chlorite,. but has another anion, it isconvenient. so to select. it so thatthe foreign salt product which; isformed will be, of. a .quitedifierent solubility: from; the. chlorate.and chlorite. Thus, if the alkaliemployed is a calcium compound, itwould be advisable to add potassium sulfate to intro-- ducethepotassiu-m ion. The calcium sulfate which is then formed may beeasily separated from the chlorite and chlorate. It should beunderstood, however, that if this foreign salt product is more solublethan calcium sulfateJ-t may still be separated from the chlorate and"chlorite-by appropriateseparation means.

However, the. invention. contemplates the selection; of such ingredientsthat the foreign salt product whichis'formed' will be recoverable with:.25 either the chlorate ,or the chlorite. This will be advantageous insome instances as this foreign salt will serve as a diluent. Forexample, by employing sodium hydroxide and potassium sulfate, the sodiumchlorite recovered can be left diluted with sodium sulfate, if desired.

In carrying out the process of the invention according to asecond mode,the alkali is used of the metal whose chlorate is desired, and after itsabsorption of chlorine dioxide until neutrality is reached, a salt of adifferent metal is added to the system. The cation of this salt should.be

the metal whose chlorite is desired. It is of'particular benefit incarrying out this procedure to employ a chlorate as the salt since thiswill result in the appearance of all, or substantially all, of the metalof the alkali as the final chlorate product. For example, if it isdesired to obtain potassium chlorate :by the use of potassium hydroxide,all of the potassium introduced into the system as the hydroxide may becaused to appear as the chlorate by adding sodium chlorate in an amountequivalent to the chlorite formed. This process takes place according tothe equations: I

In equation g, a hydroxide is employed as the alkali, but instead, anoxide, or carbonate may be employed. Also, in Equation 71. sodium hasbeen introduced by the added salt, but this metal may be selected fromthe alkali metals, alkaline earth metals, or magnesium, it beingunderstood that this metal should be selected so as to form the desiredchlorite. The precautions discussed above in reference to Equations 12and c as to the selection of the cations and anions in the system must,however, be observed.

It has been noted that the salt used to introduce the metal of thedesired chlorite need not be a chlorate. If it is not a chlorate, theforeign salt product which is formed may be separately recovered or itmay be recovered with the chlorate or chlorite.

The salt which is added should be introduced in an amount which isequivalent to half of the alkali reacted. With this relationship, anamount of metal ion is introduced which is equal to the amount ofchlorite ion which is formed so that all of this introduced cationappears as the chlorite.

If a chlorate is to be utilized in carrying out the process according tothe mode represented by Equations 9 and it, one possible source of thechlorate ion is the .products resulting from carrying out a separatechlorine dioxide absorption reaction. The products of this secondchlorine dioxide absorption reaction, after the alkali has beenneutralized, are-combined with the products resulting from theabsorption by the first alkali of chlorine dioxide. This is represented:by the It will be observed from Equations z, i, and k that anequivalent amount of alkali is consumed in the two reactions representedbyEquations i and 7'. It is not necessary that the alkalis employed inthe reactions of Equations 2 and 7' have the same anion, as the one maybe a hydroxide and the other may be a carbonate, for example.

b and. c, the process may be carried out employing any two differentmetals of the alkali metals, alkaline earth metals or magnesium, thestated precautions as :to the selection of the cations and the anions inthe system being observed.

According to a third mode of carrying out the invention, the metal ofthe alkali chosen to carry out the absorption reaction is not the metalof either. the desired chlorate or the desired chlorite, but is chosenprincipally because of the inexpensiveness of this alkali. The metal ofthe desired chlorate is introduced by one salt and the metal of thedesired chlorite is introduced by another salt. Both Of these salts areadded to the products of the absorption reaction after the alkali isneutralized and before those products of the absorption reaction areseparated.

For example, it may be desired to obtain potassium chlorate and sodiumchlorite, WithOllt the use of an alkali of either of these metals. Thismay be accomplished by using as the alkali, an inexpensive compound ascalcium hydroxide and, after the hydroxide is neutralized, adding thesalts which are to introduce the metals of the desired chlorate andchlorite. This is represented by the equations:

From Equations Z and m, it will be noted that an amount of each salt isadded which is equivalent to half of the alkali employed. This resultsin the addition of one metal in an amount equivalent to the chlorate ionformation so that all of this metal is used in the formation of thedesired chlorate. Also, it results in the addition of another metal inan amount equivalent to the chlorite ion formation so that all of thisother metal is used in the formation of the desired chlorite.

It is not necessary that the two added salts have the same anion, as,for example, one may be a sulfate and the other a nitrate. If it isdesired that the foreign salt product be separated from the chlorate andchlorite, it is preferable that the anion or anions of the added saltsbe such as to form with the metal of the alkali, a salt product of quitedifferent solubility from the chlorate and chlorite. However, this saltproduct may be left with either the chlorate or the chlorite and if thisis to be done, it may or may not have a solubility close to thesolubility of the chlorate or chlorite with which it is to appear.

The above stated precautions as to the anions and cations in the system,should be observed to assure the formation of the desired products. Forexample, if sodium chlorate is desired, the potassium ion should not bentroduced into the system.

It will be appreciated that a mixture of chlorites, for example, ratherthan a single chlorite, could be produced .by this invention simpl bythe use of two or more alkaline compounds, or .by the use ofone alkalinecompound and the salts of two or more metals. In this way, the necessarymetals for the formation of the mixture of chlorites are introduced.

Although the oxides, hydroxides, and carbonates of the alkali metals,the alkaline earth metals, and magnesium have been mentioned as thealkaline compounds useful for the operation of the invention, thereaction rate is much slower when carbonates are used than it is whenoxides llilso, as explained in connection, with Equations g-5 orhydroxides are employed. It is for this rec-.-

assume 7 son thatthe oxides and hydroxides are therpreferred alkalinematerials.

In .carring out the process of this invention in the preferred manner,chlorine dioxide as :a dilute gas in the presence of such a diluent as:air or .nitrogen, is reacted with an aqueous slurry or solution, as thecase may be, of the desired al-.- kaline .material. This chlorinedioxide is .introdnced as a dilute gas to prevent the decomposition ofthe chlorine dioxide. .Asuitable concentration of chlorine dioxide inthe gas phase is. about by volume. This concentration .depends somewhatupon the temperature employed in the reaction, the lower thetemperature, the higher the safe concentration of chlorine dioxide whichcan be allowed. The temperature of the reaction can be varied from thefreezing point to 100 C., a, suitable temperature being 50 C. The.reaction rate increases -with higher temperatures.

The quantity of water used for the reacting slurry .or solution is notvital to the operation of the invention and may be varied over a widerange. .In general, sufficient water should be present at the end of theoperation, and before the products are separated, to keep the chlorateand chlorite in solution and thereby prevent their precipitation alongwith the precipitation of the third compound, if present, providing thatit be desired to allow the third compound to be precipitated for removalfrom the chlorate-chlorite solution. If the invention is to be operatedso that only a chlorate and a 'chlorite are produced, and no foreignsalt'is to be produced, it will be evident that it is only necessary tohave suflicient water present to keep these two compounds in solution.However, if potassium -chlorate be one of the compounds produced, forexample, the amount of water present may be reduced so as to cause theprecipitation of some of the potassium chlorate. It further will berealized that should a compound, which it is desired to keep insolution, be inadvertently precipitated, additional water may be addedto redissolve it.

In general, the amount of water in the re- :action vessel, whereinchlorine dioxide is being absorbed, should be enough to make thegasiiq-uid contact efiicient. If too thick a slurry is used, difficultymay be experienced in retaining a. uniform suspension and in obtainingproper contact between the chlorine dioxide gas and the absorbingmedium. Design of the appara- :tus for the absorption of chlorinedioxide-will dictate to a large degree the optimum thickness of slurryand, therefore, the quantity-of water to be used. For most purposes, asuitable concen- 'tration of reactants is about by weight in the waterslurry or solution. This quantity .of water, for example, will keep allof the potassium chlorate of a solution containing equal moles ofpotassium chlorate and sodium chlorite solution at C.

After the reaction has been completed, the mixture of final products isremoved from the reactor for further treatment to separate the desiredproducts. Inasmuch as the reactants-and the products have been selected,as previously described, because of their mutually differentsolubilities in any given system, the separation of the various productswill entail the use of such common chemical engineering unit operationsas evaporation, crystallization, washing, and filtration.

This invention can beill-ustrated further and sorbers as a :5 by volumemixture with air.

E3 explained 'by -the following example, reference be, ing: had to: theaccompanying drawing:

In an absorber l isplaced 256.1 parts of potas+ slum. hydroxide, and-ina separate absorber 2 is placed 40 parts of sodium hydroxide, sufficientwater being used to bring them into, solution. Chiorine. dioxide-isintroduced into both ab- The reaction :is continued in each absorberuntil the hydroxide is substantially neutralized.

After both absorption reactions are completed their products "arecombined into the mixer .It will be appreciated that this may be a sepaerate vessel, or that the products of the oneab- .sorber may as well bedelivered into the other absorber. After an intimate intermingling ofthese products, they :are delivered to the evaporator 4.. Evaporation iscontinued until the solution is saturated with respect to sodiumchlorite at 125- C.

After cooling to about 25 C., the slurry from evaporator 4;is deliveredto filter 5. .About oi the 122.5 parts of potassium chlorate formed isrecovered in the filter cake, and the filtrate contains all of thesodium chlorite and the residual potassium chlorate.Theseseparatedproducts maybe dried.

Related subject matter is disclosed in my copending cases as follows:Ser. No. 647,403, filed February .13, 1946, directed to perchlorateproduction; Ser. Nos. 647,404, filed February 3, 1946', and 659,043,filed April 2, 1946, directed to the production of chlorates andchlorites; Ser'. No. 647,396, filed February 13, 1946, directed to theproduction of perc'hiorates and --involving the production of:chlorates; and :Ser. Nos. 736, 11'3, filed March 20, 1947;756542,756,543, and 756,544, filed June 23, 1947, directed to the separation ofsalts salt systems containing a chlorate and a c'hlorite.

Having thus described the invention, I-claim:

1. The process :of iorming achlorate of a metal selected fromthe classconsisting of lithium, p0- tassium, sodium, calcium, barium, strontium,and magnesium, and-for forming therewith a chlorite of a:clifh-zrentmetal selected from said class, comprising reacting chlorine dioxideand a compound selected from the group consisting of hydroxides andcarbonates, and whose metal is selected from the :class consistingoflithium, potassium, sodium, calcium, barium, strontium, and magnesium,and, after the reaction is substantially completed, combining thereaction products, without separation thereof, with a salt whose metalis adiiferent one selected from said class, whereby substantially all ofone of the metals introduced appears as the-chlorate whilesubstantially-all of the'diff-eren-t metal appears as the chlorite, saidsalt being so selected that the anion thereof does not form aninsolublecompound with the metal whose chlorate isdesired, and saidcompound and said salt being so selected that no potassium ion ispresent when a chlorate other than that of potassium is desired.

2. The process of forming a chlorate of a metal selected .from the classconsisting of lithium, potassium, sodium, calcium, barium, strontium,and magnesium, and for .forming therewith a .chlorite of a diiferentmetal selected from said class, com.- prising reacting chlorine dioxideand a compound selected from the group consistin of hydroxides andcarbonates, and whose metal is selected from the class consisting oflithium, potassium, sodium, calcium, barium, strontium, and magnesium,and, after the reaction is substantially completed, combining thereaction products, without separation thereof, with a salt of the metalwhose chlorate is desired, whereby substantially all of this lattermetal appears as the chlorate, said salt being so selected that theanion thereof does not form an insoluble compound with the metal whosechlorate is desired, and said compound and said salt being so selectedthat no potassium ion is present when a chlorate other than that ofpotassium is desired. v 1

3. The process of forming a chlorate of a metal selected from the classconsisting of lithium, potassium, sodium, calcium, barium, strontium,and magnesium, and for forming therewith a chlorite of a different metalselected from said class, comprising reacting chlorine dioxide and acompound selected from the group consisting of hydroxides andcarbonates, and whose metal is selected from the class consisting oflithium, potassium, sodium, calcium, barium, strontium, and magnesium,and, after the reaction is substantially completed, combining thereaction products, without separation thereof, with a salt of the metalwhosechlorate is desired, whereby substantially all of this metalappears as the chlorate, said salt being introduced in an amountequivalent to half the compound introduced, said salt being so selectedthat the anion thereof does not form an insolublecompound with the metalwhose chlorate is desired, and said compound and said salt being soselected that no potassium ion is present when a chlorate other thanthat of potassium is desired.

4. The process of forming a chlorate of a metal selected from the classconsisting of lithium, po-

tassium, sodium, calcium, barium, stronti um,'and

said chlorate being so selected that no potassium ion is present when achlorate other than that of potassium is desired.

5. The process of forming a chlorate of a metal selected from the classconsisting of lithium,v Dotassium, sodium, calcium, barium, strontium,and magnesium, and for forming therewith a childrite of a differentmetal selected from said class, comprising reacting chlorine dioxideand. a compound selected from the group consistingof hydroxides andcarbonates, and whose metal is selected from the class consisting oflithium, potassium, sodium, calcium, barium, strontium, and magnesium,and, after the reaction is substantially completed, combining thereaction products, without separation thereof, with a chlorate whosemetal is a different one selected from said class, whereby the metal ofsaid compound appears as the metal of this introduced chlorate ion, saidchlorate being added in an amount equivalent to half the introducedcompound, and said compound and said chlorate being so selected that nopotassium ion is present when a chlorate other than that of potassium isdesired.

6. The process of forming a chlorate of a metal selected from the classconsisting of lithium, potassium, sodium, calcium, barium, strontium,and

magnesium, and for forming therewith a chicrite of a different metalselected from said class, comprising reacting chlorine dioxide and acompound selected from the group consisting of hydroxides andcarbonates, the metal of the selected compound being that of the desiredchlorate, and, after the reaction is substantially completed, combiningthe reaction products, without separation thereof, with a salt Whosemetal is selected from said class and whose chlorite is desired, wherebysubstantially all of the metal introduced as the salt appears as thechlorite, said salt being so selected that the anion thereof does notform an insoluble compound with the metal whose chlorate is desired, andsaid compound and said salt being so selected that no potassium ion ispresent when a chlorate other than that of potassium is desired.

7. The process of forming a chlorate of a metal selected from the classconsisting of lithium, po-

tassium, sodium, calcium, barium, strontium, and

magnesium, and for forming therewith a chlorite of a difierent metalselected from said class, comprising reacting chlorine dioxide and acompound selected from the group consisting of hydroxides andcarbonates, the metal of the selected com pound being that of thedesired chlorate, and, after the reaction is substantially completed,combining the reaction products, without separation thereof, with a saltwhose metal is selected from said class and whose chlorite is desired,whereby substantially all of the metal introduced asthe compound appearsas the chlorate, said salt being added in an amount equivalent to halfthe compound introduced, said salt being so selected that the anionthereof does not form an insoluble compound with the metal whosechlorate is desired, and said compound and said salt being so selectedthat no potassium ion is present when a chlorate other than that ofpotassium is desired.

' 8. The process of forming a chlorate of a metal selected from theclass consisting of lithium, potassium, sodium, calcium, barium,strontium, and magnesium, and for forming therewith a chlorite of adifierent metal selected from said class, comprising reacting chlorinedioxide and a compound selected from the group consisting of hydroxidesand carbonates, and whose metal is selected from the class consisting oflithium, po-- tassium, sodium, calcium, barium, strontium, andmagnesium, and, after the reaction is substantially completed, combiningthe chlorate and chlorite, without separation thereof, with theunseparated chlorate and-chlorite resulting from the reaction ofchlorine dioxide with a compound whose metal is a different one selectedfrom said class, whereby the major portion of the metal of the onecompound appears as a chlorate and the major portion of the metal Of theother compound appears as a chlorite, and said compounds being soselected that no potassium ion is present when a chlorate other thanthat of potassium is desired.

9. The process of forming a chlorate of a metal selected from the classconsisting of litmium, potassium, sodium, calcium, barium, strontium,and magnesium, and for forming therewith a chlorite of a different metalselected from said class, comprising reacting chlorine dioxide and acompound selected from the group consisting of hydroxides andcarbonates, and whose metal is selected from the class consisting oflithium, potassium, sodium, calcium, barium, strontium, and magnesium,and, after the reaction is substanaccepts :12 .ot. acdiflerent metalselected from saidclass, com- .ipfis'ingreadtingchlorine dioxide. and acompound selected from the 'groupconsisting of hydroxides andcarbonates,- and whose metal is selected from ".the class. consistingoflithium, potassium, sodium, calium, barium, strontium, and magnesium,and, after the reaction is substantially completed, combining .thereaction products, without separation'thereoiwith two salts, the metalof onasalt i q amounts on an equivalent s, a 4 being that, or .thedesired chlorate and the metal "said compounds being so selected that nopotassiumion is present-when a chlorate other than that of potassium isdesired.

10.'The process ofjforming a chlorate of a. metal selected from theclass consisting of lithium,

potassium, sodium, calcium, barium, strontium,

and magnesium, and for forming therewith a chlorite of a difierent metalselectedfrom said class, comprising-reacting chlorine dioxide and acompound selected. from the-group consisting-of hydroxides andcarbonates, and whose metal, is selected from the class consisting oflithium,-potassium, sodium, calcium, barium, strontium, and magnesium,and,. after the reaction issubstantially completed, combining thereaction products, without separation thereof, with .a chlorite .of ametal whose chlorate is desired, whereby .sub- 'stantially all of this.latter .metal appears-as .the chlorate and all of the metal of thecompound appearsas achlorite, and said compoundand said chlorite beingso selected that nopotassiumionis present when a. chlorate otherthanpotassiumis desired.

'11. Theprocess of forminga chlorate ofaimetal selected from theclass-consisting oilithium, .po-

tassium, sodium, calcium, barium, strontium, and magnesium, and forforming therewitha chlorite of a differentmetal selected from saidclass, comprising reacting chlorine dioxide .an'da compound selectedfrom the group consisting of hydroxides and carbonates, and whosemetalis selected from the class consistingofflithium,.potassium, sodium,calcium, barium, strontium and magnesium, and, afterthe reaction issubstantially completed combihing the reaction .products, withoutseparation thereof, with achlorite ofvametal whose chlorate is desired,whereby substantially all of this :latter metal appears asthe chlorateanddall-of .the metal of the compound appears asa chlorite,.saidch1oritebeing introducedv in an amount equivalent to half the compound'introduced,.and-said compound and said chlorite being so selected thatnopotassium'ion ispresentwhen a chlorate-other than potassium isdesired.

'12. The process of 'forminga chlorateofiametal 'selectedffrom the.class consisting of lithium,.-potassium, sodium, calcium, barium,strontium and magnesium, and for forming .therewitha chlorite of theother salt'being that of thedesired chlorite, .th'e metallsof-theseisalts'being different from eticlii dthenand from the metal ofvsaid compound. but beingselec'ted from said class, said salts being-so:selectedthatthe anions thereof do not form insol- "uble compounds withthe metal whose chlorate is"desired,,and'said compound and saidsaltsbeing 'so'selected that Sno potassium ion is present when a-chlorate other thanthatofpotassiumiis desired.

"1'3.".'1he;process of forming a chlorate of a metal selectedfrom theclass consisting. of lithium,.potassium, sodium, calciumjbarium,strontium, and

magnesium, and'foriorming therewith a chlorite of a different metalselectedfrom said class, comprising-reacting chlorine dioxide and acompound selected "from theg'roup consisting ofv hydroxides andcarbonates, "and whose metal is selected. from the class consisting oflithium, potassium, sodium, calciumjbarium, strontium, andmagnesium,and, after the reaction is substantially completed, combining thereaction products, without separation thereof,'with'two salts, themetal. of one salt being thatof the desired chlorate. andthemetalofthedther saltbeing that of .the desired chlorite, the metalsofthesesalts being different fromeach "other and "from the .meta1 ofsaid, compound'but being selected fromsa'id class, each of said saltsbeingdn'troduce'diin an. amount equivalent to half thecomp'ound'reacted, said salts being soselected :that 'th'e'ariionsthereof. :do not form insoluble compounds with the metal whose chlorateis desired-and said compound and said salts being so selectedth'a'tnospo'ta'ssium ion is "present when a chlorate other-"thanthat'ofpo'tassium. is desired.

CLIFFORD A. HAMPEL.

REFERENCES 'Iheiollowlng references (are .of record in the file of thispatent:

UNI I ED STATESPKI'EN I S Number Name Date {2,046,830 .Logan -July 7,.1936 "21.691166 Cunningham and Aug. 8, 1939 :O'ITI-IEIR' REFERENCES"Mllbr, Comprehensive .Treatise 'on Inorganic andTheoretical'Chemistry,vol."2, p. 282 (1922).

